Flexible or rigid combinations of materials in composite form which are formable and adhesive at temperatures below 90° C.

ABSTRACT

Combinations of materials in composite form, which are thermoadhesive to themselves by treatment at temperatures not exceeding 90° C. and which can be shaped in the form of a laminate at said temperature, are characterized in that they comprise an open mesh textile substrate first impregnated or coated with a first rubber-like elastoviscous constituent having a softening point not exceeding 90° C. and further coated with a second, semi crystalline constituent essentially of polyester type having a fusion temperature from 35° to 80° C. These combinations have controlled adhesiveness and adequate fluidity for easy application by hand, particularly in do-it-yourself applications, orthopedics, sport and physiotherapy.

This invention relates to new composite combinations, in sheets,plaques, strips or laminates that are thermomalleable and thermoadhesiveto themselves, flexible or rigid, with rather short setting time, and topreparation processes of those composite combinations.

Besides usual applications of plastics, there are various potentialdomains of applications wherein it is required to realize at everyoccasion a unique part or assembly with a material that one desires tomold, form or shape preferably manually and with a simple pre treatmentsuch as heating at an easily accessible temperature.

Through the preparation treatment for their use, those materials musttherefore have an adequate formability as well as an adhesive potentialto themselves. The herein envisioned preparation treatment is limited toa temperature conditioning which will be detailed later, excluding theuse of any solvent or external adhesive.

The application being in view can bear on an object or a creation asrigid as possible or one can seek in the application for some degree offlexibility to be selected according to the situation.

Such applications are often sought by individuals having not necessarilya great dexterity, who are willing to practice themselves withoutsophisticated technical means, realizing the molding, the shaping or theassembly principally by hand with the eventual help of a few simpletools such as scissors, clamps and holders. Obviously, the applicationsin view here can also be practiced by professionals operating in anindustrial environment but that is not required.

As a result those forming and laminating applications must be realizedfrom a pre-treatment temperature that remains accessible without risk ofburns or other disadvantage that may cause clumsiness or an accident.

The used material must lose its adhesive property once it returns toambient temperature and also keep the shape it was given and it must becapable to withstand mechanical stresses to which it may be exposed andnot lose its shape up to a temperature as high as possible governed bythe application.

A pre-treatment temperature range from 40° C. to 80° C. seems to besuitable, In any case under 100° C. so that such preparation can be doneeasily and relatively quickly by using hot water for example. It makessense that alternative heating sources can be used also such as thethermal oven, the heat gun or the microwave oven.

Considering the applications in view, it is also recommended that thosematerials are inert and do not release substances that are toxic,irritating or with another noxious character so that the user can applythem without any particular safety mean.

Those products must also be stable for a long period of time withoutbeing subject neither to chemical ageing nor preferably to any physicalageing.

Therefore it should not be necessary to have to use sophisticatedpackaging such as hermetically sealed pouches subjected to tearing andthat compromise the use of the material once the pouch has been openedas it can be the case in the application of the european patent 0 413399 A1.

There are already a few domains of applications of the type of productaddressed by this invention where one uses composites that arethermoformable and thermoadhesive as from a temperature of treatmentfrom about 70° C. to 80° C. and that are essentially restricted to useswhere a high rigidity is looked for. This concerns principally thephysiotherapy where splints, orthoses and other means of rigid supportare already made like that, the orthopedics interested with saidthermoplastic bandages for cylindrical casting or with externalprostheses made of same material, but also the field of decoration wherestage scenery, masks and various objects essentially in three dimensionsare made like that by laminating 2 or more layers.

In order to obtain the effect of formability and adhesiveness in thedesired temperature range, one has principaly linear polymers of cyclicesters characterized by "COO" moieties apart one to another withmethylene radicals comprising 2 to 7 carbon atoms of which the principalavailable representative is the polymer of 2-oxepanone better knownunder the popular name of polycaprolactone (PCL). The U.S. Pat. No.3,692,023 suggests the use of that polymer to obtain immobilizationdevices from a substrate coated with the polymer and the french patent2,376,170 leads to the same results by a just better performing process.In other respects, the U.S. Pat. No. 4,273,115 recommends a particularRaschel knitted fabric partially impregnated with that PCL polymerhaving a molecular weight of about 40 000 as material for cylindricalcasting. Finally, in the U.S. Pat. No. 4,316,457, one has proposed thepreparation of a linear thermoplastic polyurethane having a molecularweight from 40,000 to 45,000, synthesized in two steps where aprepolymer based on two moles of diisocyanate and one mole of polyesterdiol is added with one mole of polyester diol prior to impregnation of aRaschel knitted web to build chain extension while completing thepolymerization on the latter at same time as the solvent is removed.

As they are described, those polyesters become fluid at the melttemperature and have an excessive adhesiveness on any object to whichthey come in contact in the melt state. This adhesiveness in the meltstate that leads to transfer of material does nevertheless disappearafter hardening under cooling. Therefore the use of those polyesters inorthopedics has required various adaptations and one can observe thatthe condensation polyesters behave the same way.

In the U.S. Pat. No. 3,692,023, one uses a soft underlayer to keep thepolymer out of sticking to the skin and hair that it covers when it isapplied onto. In the same Patent, it is considered to preens the samepolymer in sheets on a support or as a sandwich made of a knitted, wovenor non-woven fabric with the assigned role is to prevent the flow of thematerial in the melt state. In the U.S. Pat. Nos. 4,273,115 and4,316,457 pertaining to orthopedic bandages, one uses a polyethyleneseparator film which is wound together with the bandage to prevent itstransformation in a mass at the time of its application. The U.S. Pat.No. 4,143,655 recommends another type of separator having multipleopenings whereas the U.S. Pat. No. 4,454,873 allows to eliminate thebothering effect of a separator by the coating of an nonadherant andhydrosoluble polymer film on the material of the bandage itself.However, the latter solution has the drawbacks of progressivecontamination of the water in the preparation hydrocollator and ofsignificant reduction of the interlaminar strength between the variousplies in a cylindrical cast in particular.

There are also physical adaptations which are inside the materialcontaining those polyesters, It could be observed indeed that the typeof Raschel knitted fabric with bulky strands made of shortcut fibersdescribed in the U.S. Pat. No. 4,273,115 and 4,316,457 is absolutelynecessary to suppress the effect of the to large fluidity of thepolycaprolactones and of the linear polyurethanes related to, whenapplied in an orthopedic bandage for example. Those largely open strandshave a very low apparent density and offer a volume between the fibersof about 80 per-cent. The U.S. Pat. No. 4,273,115 specifies moreoverthat the strands of fibers can only be partially impregnated with thepolymer. The mechanical strength of those strands necessarily littletied up and partially impregnated is therefore rather weak and that canbe seen in particular on the finished product impregnated with the resinand that can be easily torn by hand. The strand elements being so coatedwith polymer, the entirety is opposed to the fluid flow of thethermoadhesive constituent. However the latter remains highly deformablein a plastic manner, and the use of a roll of this material treated atthe right temperature leads rapidly to a dense mass which becomes veryhard to unwind if a separator polyethylene film has not been wound inthe roll together with the bandage itself.

The new objectives presently aimed for in the applications based on thisknow-how are not satisfied by these aliphatic polyesters or these linearpolyurethanes related to if they are applied separately.

Indeed, if one tries to apply the polymers described in the U.S. Pat.No. 4,273,115 and 4,316,457 onto a fabric or a knitted web havingespecially open mesh, and being of high tenacity which is possible onlyif strands are selected being more tightened, better tied up and made ofcontinuous fibers, one must, in order to end up with the same surfaceweight of thermoadhesive resin, coat to a greater extent the outsidepart of the strands from which the resin which is no longer held by thefibers. It can then move in an undesirable manner and be transferred onthe tools or the hands of the user during the application.

Moreover the knitted webs with bulky strands as recommended in thosepatents are soft to a point that they cannot be handled in a width underabout one meter. Under those circumstances already, there is a narrowingof the warp strands caused by the traction and the weight when they areimpregnated with the usual vertical processes also described in the samepatents. Bandages of usual width are thus obtained in this case, byslitting the product after its impregnation in full width and drying.Such slitting operation results in sharp edges at the point wheretransverse threads have been cut. There is an obvious interest to obtaina bandage in useful width with uniform edges free of unevenness.However, with the textile construction that is required by the polymersdescribed in the referenced patents, narrow width strips cannot holdthemselves sufficiently and the final product comes out substantiallynarrower than at the beginning. Moreover, one observes concurrently withthis type of bulky knitted web made of strands with short fibers, anelongation in the other direction which comes back at the time ofheating for use preparation. Thus the textile substrates necessary forthe polymers of the prior art do not allow a dimensionally stableproduct and it is necessary to prepare the strips by slitting after thepolymer has been applied. If in other respects, one is interested withthose impregnated knitted webs, not in view of a cylindrical cast but inview of laminated sheets for splints or orthoses, the user must takeaccount for the shrinkage, sometimes up to 10 per-cent that arisesduring the preparatory heating of the sheet and this is inconvenient.There is therefore, an interest to use less deformable fabrics.

Knowing that tile applications of the products envisioned in the presentinvention comprise a cycle of heating and cooling, it is useful todefine at least four characteristic temperatures of which it is alsointeresting to examine the values to appraise the advantages provided bythe invention beyond the simple control of fluidity and adhesiveness.

The softening temperature (T1) is the temperature at which the materialstarts to lose its rigidity. In particular, it can be determined by theASTM method No. 1043-87 or 1053-89 taking the inflection point of thecurve of variation of modulus with temperature.

The treatment temperature (T2) for the application is the suitedtemperature at which it is required to bring the material In order thatit has In an appropriate time, the desired formability and adhesivecharacteristics and retains them sufficiently during the time necessaryto complete the application. It has to be noticed that during theapplication, the material cools by either a natural or forced way.Depending on the thickness of the material and the ambient temperature,that T2 temperature will be more or less high, necessarily above the thethermodynamic melting temperature of the semi-crystalline constituent inthe combination.

The temperature (T3) is the temperature at which, during the cooling ofthe material, normally after completion of the application, the materialstarts losing its adhesive capability.

The temperature (T4) is the temperature at which, during the cooling ofthe material, normally after completion of the application, the materialstarts losing its capability to be shaped due to the increase of itsrigidity.

In practice, one refers more often to the time (t3) after which thematerial is no longer adhesive and the time (t4) after which thematerial is no longer formable when it cools down in given thickness, ina given ambience and having applied a given treatment temperature. Insuch case, there is a parallel between t3 and T3 as well as between t4and T4.

This distinction of the above four temperatures allows to specify theoptimal characteristics of the envisioned products from that point ofview.

In a general manner, the temperature T1 should be as high as possibleabove room temperature, temperature T2 should be as low as possible toallow easy application without risk of burns, which is particularlyimportant in the instance of an orthopedic bandage. The temperature T3should be as low as possible to provide the operator with a maximumdelay t3 during the application. The optimal value of T4 depends on theapplication and on the time t4 the operator wants to have to completehis task. Time t4 must be sufficiently long but not to the point theoperator has to wait for the evaluation of his work.

About those characteristic temperatures, let us notice that the GermanPatent DE-3605192 A1 suggests a mean to obtain precisely the shaping ofa thermoadhesive sheet, which is not aimed to be laminated but rather toassemble shoe parts, at a temperature as low as possible under thetemperature at which the sheet becomes adhesive, and this by a nontotally covering coating only with a thermoadhesive product, of asubstrate eventually impregnated by a polymer. It goes without sayingthat this know-how which targets in our nomenclature a maximum gapbetween T1 and T2, is not applicable in the domains envisioned by thepresent invention where one seeks, on the contrary, a dimensionalstability of the composite in the largest temperature interval aspossible.

The object of the present invention is to provide materials becomingeasily moldable by hand up to large sizes of one square meter or two,after a treatment at the lowest possible temperature under 100° C.,while retaining the properties at room temperature up to a temperatureas high as possible above room temperature.

Another object of the present invention is to provide those materials inthe form of thermoplastic orthopedic bandages, lightweight and aerated,exhibiting, without having to count on an inter-layer separator film, agood interlaminar strength, a good rigidity and a good resistance totearing, such that the roll does not transform in a dense mass nortransfer the resin it contains on objects other than itself during Itshot application.

Another object of the present invention is to provide also thosematerials in the form of bandages soft or semi rigid that can belaminated after some temperature treatment and that become non stickyagain when cold.

Another object of tile present invention is to provide those compositesin the form of composite plaques or sheets easily moldable and adhesiveto themselves, and which retain their shape as the molding progresseswithout risk of uncontrolled deformation due to exaggerated fluidity, sothat a single operator can laminate a large size part such as alombostat, a stage scenery or the negative print of an object on theaverage larger than a meter.

Another object of the present invention is to obtain those compositeswith inexpensive processes using as little as possible or no solvent.

Another object of the present invention is to make those materialsrecyclable and reusable.

In the present invention, one has obtained several means to control thefluidity at T2, the adhesiveness, the rigidity and the characteristictemperatures of thermoadhesive composites in the form of plaques, sheetsor yet textiles with open mesh coated with such materials, formable andmoldable under the conditions described above, of an easy working at atemperature that does not impede manual application in particular.

According to the present invention, it was found surprisingly that somecomposite combinations, of amorphous or semi-crystalline polymerstructures that have a viscoelastic to rubbery behavior above a certaintemperature, with a varying proportion depending on the application, ofthermoplastic polymer structures, essentially semi-crystalline andcomprising a minimum amount of aliphatic ester structural units, allowto overcome the difficulties cited above of a to large fluidity and ofexcessive adhesiveness, while providing new possibilities to modulatethose characteristics as well as other useful characteristics in theapplication or use of resulting materials.

In the continuation of this description, one will name "firstconstituent" and "second constituent" respectively, the two abovedefined constituents of the combination as they are applied in sequenceon a textile or plastic substrate.

The combination of the present invention comprises a first amorphous orsemi-crystalline polymer constituent that is above its heat softeningpoint at least at the temperature T2 and exhibiting at that sametemperature at least a viscoelastic to rubbery behavior, and anessentially semi-crystalline second constituent with a content ofaliphatic ester type structural units of at least about 80 per-cent andexhibiting at the temperature T2, an essentially plastic behavior, andsuch that the first constituent is applied in the first place on thesubstrate of the composite and the second constituent at the last place,forming a continuous film or covering completely the strands if, forexample, the substrate is a knitted fabric with open mesh.

The combinations as described here before were found to bethermoadhesive in a fully satisfactory manner, without showing theinconvenience of uncontrolled deformation during the application.Through the selection of the proportion and the elements of the firstconstituents, and also to some extent by the selection of the elementsof the second constituent, it has been observed that it was alsopossible to adjust the characteristic temperatures, the flexibilityduring the application and the rigidity of the finished productaccording to the needs.

According to the present invention, the second constituent is selectedsuch that it has intrinsic thermoadhesive properties whereas the firstconstituent does not have them necessarily. Inversely, one has foundthat the first constituent has to provide the combination with aviscoelastic behavior when it is subjected to the temperature of thepreparation treatment, which has been obtained with some firstconstituents having themselves a viscoelastic to rubbery behaviorwhereas the second constituent is only plastic at the same temperature.

In this manner, it was surprising to note that strips based on a knittedfabric with open mesh, impregnated firstly with a latex of a copolymerbased on an acrylate, methacrylate, vinyl ester or of another polymer orcopolymer having a heat softening temperature between (-40)° C. and(+60)° C., then dried, then covered with a polymer solution based onpolycaprolactone or other means leading to a semi-crystallinethermoplastic polymer comprising at least 80 per cent of aliphatic estertype structural units, give, after evaporation of the solvent, a bandagethat can easily be wound up and that, after immersing in a water bathset at 70° C., can be unwound without difficulty, whereas the same stripimpregnated with the same equivalent total weight of the samepolycaprolactone becomes an indivisible mass if an inter-layer separatorpolyethylene film has not been put in place and this is surprising sincethe contact material at the interface is then identical in both cases.

In this embodiment of the invention, one has found that the rigidity ofthe dry bandage when it is finished, is directly related to thesoftening temperature of the first constituent, stiffer than a noncomposite bandage if the softening temperature of the first constituentIs above about 15° C. and less rigid in the opposite case.

In a first group of polymers used as the first constituent, the group ofvinyl and acrylic or methacrylic ester polymers and copolymers appearedto be particularly interesting.

In this composite presentation of the material, the first constituent ofvinyl, aczcylic, methacrylic or dienic type, is applied by impregnationor coating of a textile substrate in the first place, and It is thencovered by the second constituent. Following this embodiment of theinvention, a preferred embodiment is to apply this first constituentunder the form of an aqueous dispersion such as a latex of the polymeror of the copolymer. One can this way apply a large quantity of solidmatter without negative environmental impact. The second constituentcovering the first one can be applied different ways, for example, bylaying a polymer solution or a solution of monomers leading to theformation of the polymer on the substrate during or after theevaporation of the solvent.

This preferred embodiment of the invention gives access to a greatvariety of products such as thermoadhesive bandages which stay flexibleand non sticky at room temperature if one chooses for the firstconstituent a latex of a polymer having a glass transition temperatureunder about 15° C. and in particular of about (-20)° C., or large sizeimmobilization devices which are relatively little deformable attemperatures between T2 and T4 so that they easily keep the shape thatis given during the time t4 and which are of high rigidity at roomtemperature, if, on the contrary, one chooses for the first constituent,a latex of a polymer having a glass transition temperature in theinterval T2 and T4, that is to say for example at about 40° C. as it canbe obtained for example from emulsion polymerisation ofisobutylmethacrylate or of a mixture of methylacrylate andethylmethacrylate.

The combination possibilities are so many in this embodiment of theinvention that it is not possible to tell them all. They allow inparticular as already noted above, to obtain a product for which T3 isunder T4 and this is unattainable with the prior art. One has been ableto obtain such characteristics by applying a quantity above 50 per centof a first constituent of the type of polyethylmethacrylate made inemulsion, then covering the latter with the second constituent based onpolycaprolactone. After a treatment at 75° C., one sees the material isstill adhesive while it has become almost rigid.

With this particular embodiment of the invention, one obtains inparticular, bandages or composite products for splints, orthoses orother application, that can be either softer or stiffer than thoseprovided by the prior art and having in the latter case, the capabilityto adjust the flexibility of the material for the time when it will betransformed, that is to say in the time interval t4.

In a second group of polymers used as the first constituent, it wasfound that It was possible to obtain the same effects with a copolymersuch as, for example, of the polyurethane or polyurea type which has aviscoelastic to rubbery behavior at least at temperature T2 and in theinterval T2 to T4, and eventually under T4 depending on the fact thatthe characteristics of this polyurethane govern the temperature T4 orthat the latter is governed by the characteristics of the secondconstituent respectively.

One obtains the same type of effect as with the first constituents ofvinyl or (meth)acrylate type.

One obtains fairly easily this constituent being viscelastic to rubberyat least a temperature T2, by reaction of a mixture of diol, triol anddiisocyanate in particular, but one can obtain it also from bifunctionalreagents only if in particular, one of them is intrinsically rubberylike polytetramethyleneglycol or a polypropyleneoxide. One can obviouslyuse at the same time a triol and a rubbery diol.

This second type of first constituent of polyurethane nature, canmoreover be amorphous or semi-crystalline at room temperature but inthis latter case, its softening temperature must be under the envisionedT2 temperature, thus in any case under about 95° to 100° C. andpreferably under 80° C. It goes without saying that the urethanereaction is not indispensable to form this type of first constituent inthe combination and that any other chemical link can be suited.

In a preferred embodiment of the invention according this second familyof first constituents, in particular if one seeks to obtain at roomtemperature a rigidity as high as possible, one chooses a polyurethanecontaining at least about 50 per-cent of crystallizable structural unitsand having a melting temperature under T2, such as based on an aliphaticester having a molecular weight of at least about 2000 and preferablyabove 3000.

These combinations bear several decisive advantages in particular withrespect to cyclic ester polymers alone as well as to linear urethanehomopolymers of the prior art which as recalled above, require the typeof substrate with bulky strands as well as a separator film for thewinding of orthopedic bandage rolls.

It should also be noted that the present invention enlarges considerablythe spectrum of resulting applications. It allows in particular toobtain a soft thermoadhesive bandage that proves to be useful for thetreatment of a dislocation such as of the tendons.

In this application in a composite form representing the embodiment ofthe present invention, such as bandages or immobilization devices basedon a textile substrate with open mesh in particular, it is also possiblefor the second group of first constituents, to dissociate the twoconstituents in a combination such that the first constituent of aviscoelastic to rubbery nature is laid or impregnated first and thesecond thermoadhesive constituent is laid next in a continuous film oras a complete envelope around the strands of a knitted fabric with openmesh. One obtains a similar effect and in a same way as when the firstconstituent is of polyvinyl or poly(meth)acrylate type.

For the two groups of first constituents, the ratio between the amountof the second constituent to the amount of the first one must beadjusted depending on the rubbery character of the first one, In a waythat ensures a sufficient adhesive Joint, If the first constituent hascharacteristics of a relatively little deformable rubber, then anoverall quantity of thermoadhesive second constituent greater than 50per cent may be necessary for the possible contact area for laminationis relatively low. If the first constituent exhibits a sufficient:plasticity between T2 and T4, then an amount of second constituent lessthan 50 per cent may eventually be sufficient. From a simple geometricreasoning, indeed, one easily understands that a quantity of 49 per centof first constituent for example leads, due to the concentric covering,to a thickness of the second constituent which is 30 per cent of theradius only, if the volume occupied by the textile is not taken intoaccount. Therefore it is not surprising that this technique requiresnevertheless a relatively large weight portion of thermoadhesiveconstituent, its effect being diminished by the geometry. As opposed towhat could be expected however, one had to note that the stiffnessproperties of the resulting laminated composite are principally governedby the characteristics of the first constituent, and this is surprisingIf we think In terms of the strength of materials theory. Indeed, ifreduced to a unit mass, a hollow pipe is always stiffer than a full rod.

It must hence be the composite effect after laminating that governs thisrigidity. One has indeed obtained with this embodiment of the presentinvention, a composite material where the stiffness of each individualply during the transformation (between T2 and T4) is lower than the oneof an equivalent ply with a homogeneous composition, whereas themultiplies resulting composite is surprisingly found to have a greaterstiffness.

In a general manner, the applications of the products of the presentinvention are much larger than those of the prior art. One can obtainmaterials indeed that are easily worked by hand, into circular casts,orthoses, external and supporting prostheses as well as softthermoadhesive bandages which were not previously known. Furthermore,large size decorative structural elements are possible.

The thermoplastic orthopaedic bandages in particular can be directlyfabricated in useful widths of 5, 10, and 15 centimeters for example andbe finished with smooth and uniform edges. The thermoplastic splints andorthoses obtained by impregnation of a cloth can be, according to thepresent invention, dimensionally stable for the latter allows to useknitted fabrics with continuous fibers threads which are ratherentangled, thereby preventing elongation during the impregnationprocess. In another respect, this embodiment of the present inventionallows if one desires, to reinforce a more deformable fabric by firstimpregnation with a polymer as described and in particular, in the formof a latex for example.

The present invention allows one to vary the characteristic temperaturesin a much larger range than with the prior art and obtain variableflexibility's and rigidities of the material not only during itsapplication but also after it has set.

EXAMPLES

On a polyester cotton knitted fabric with 6 mm mesh size and weighing151 g per square meter, one has applied successively by a dippingprocess, latex of acrylate-methacrylate copolymers with glass transitiontemperature of 11° C., 28° C. and 41° C. respectively. The dry stripswere then covered by impregnation with a solution in methylenechloridecomprising 483.8 g of polycaprolactone diol of molecular weight 4280,3.4 g of polycaprolactone triol of equivalent weight of 184, 19.7 g ofhexamethylenediisocyanate, about 300 g of solvent and 0.15 ml ofdibutyltindilaurate. After oven treatment at 95° C., one obtainsbandages with proportion of constituents given in the table 1, where isalso given the glass transition temperature of the latex polymers andthe apparent modulus after lamination of the bandage in three layers at65° C.

                  TABLE 1                                                         ______________________________________                                        Weight ratios and flexural rigidity in relation with                          softening temperature of the first layer.                                     ______________________________________                                        Softening temperature                                                                         11° C.                                                                           28° C.                                                                         41° C,                               Fabric weight fraction                                                                        0.17      0.17    0.17                                        First layer weight fraction                                                                   0.24      0.29    0.29                                        Second layer weight fraction                                                                  0.59      0.54    0.54                                        Apparent flexural modulus                                                                     156       242     380                                         (3 laminated plies) (MPa)                                                     ______________________________________                                    

The three types of strips wound in 2 meter long rolls and without aseparator film, behave properly in the application on a limb when theyhave been treated In the water at 60° C. for one minute and form afterabout 5 minutes, a soft or rigid bandage depending on the softeningtemperature of the first constituent which is 11° C. in the first caseand 41° C. in the latter.

I claim:
 1. A composite composition of materials in flat or wound sheetoffering uniformly distributed openings of size from 1 to 12 mm, leavinga free passage of at least 20 percent of the total surface, formable andadhesive to themselves at a temperature in a temperature interval from35° C. to 90° C., and combining an open mesh textile substrate withspecific weight not exceeding 500 g per square meter, whose body issuccessively impregnated or coated, then impregnated again andcompletely covered with at least two distinct materials, the first one,inside or on the surface of the substrate being of the group of polymershaving a softening temperature not exceeding 80° C. and showing abovethat softening temperature a viscoelastic to rubbery but non fluidbehavior, and the last one at the outer surface of the first ones, beingof the group of semi crystalline polymers with a content of aliphaticester type structural units of at least 80 percent and having a meltingtemperature comprised between 35° and 80° C. and having during a certaintime after the fusion of an adhesive character on itself in a away thecombination can be laminated in 2 or more layers.
 2. A combinationaccording to claim 1, wherein the substrate is an open net with meshsize from 1 to 12 mm.
 3. A combination according to claim 1, wherein thesubstrate is an open knitted fabric with mesh size from 1 to 12 mm.
 4. Acombination according to claim 1, wherein the substrate is an open wovenfabric where warp and weft threads leave openings from 1 to 12 mm.
 5. Acombination according to claim 1 wherein the substrate is a non wovenfabric whose structure leaves openings from 1 to 12 mm.
 6. A combinationaccording to claim 1, wherein the substrate is a woven or non wovenfabric perforated or expanded with openings from 1 to 12 mm.
 7. Acombination according to claim 6, wherein the first material is appliedon the substrate before expansion or perforation.
 8. A combinationaccording to claim 6, wherein all the materials are applied on thesubstrate before expansion or perforation.
 9. The combination accordingto claim 1 wherein the first material is in weight proportion of 10 to90 per-cent and the second in weight proportion of 90 to 10 per-cent,the substrate weight being from 5 to 50 per-cent that of the wholecombination.
 10. The combination according to claim 1 wherein the firstmaterial is in weight proportion of 20 to 90 per-cent and the second inweight proportion of 80 to 10 per-cent, the substrate weight being from5 to 50 per-cent that of the whole combination.
 11. The combinationaccording to claim 1 wherein the first material is in weight proportionof 10 to 80 per-cent and the second in weight proportion of 90 to 20per-cent, the substrate weight being from 5 to 50 per-cent that of thewhole combination.
 12. The combination according to claim 1 wherein thefirst material is in weight proportion of 20 to 80 per-cent and thesecond in weight proportion of 80 to 20 per-cent, the substrate weightbeing from 5 to 50 per-cent that of the whole combination.
 13. Acombination according to claim 1 wherein the first material at least isa vinyl polymer or copolymer.
 14. A combination according to claim 1wherein the first material is a polymer or a copolymer of acrylic ormethacrylic ester.
 15. A combination according to claim 1 wherein thefirst material is a polymer or a copolymer of butadiene, chloroprene orisoprene.
 16. A combination according to claim 1 wherein the firstmaterial is a copolymer of styrene or acrylonitrile with butadiene orchloroprene or isoprene.
 17. A combination according to claim 1 whereinthe first material is a copolymer of ethylene and acrylic, methacrylicor vinyl ester.
 18. A combination according to claim 1 wherein the firstmaterial is a thermoplastic polyurethane.
 19. A combination according toclaim 1 wherein the first material is a polyurethane or a polyurea. 20.A combination according to claim 1 wherein the first material is abranched or partially or totally cross-linked polymer and comprises inproportion larger than 50 per-cent the structural unit of crystallizablealiphatic polyesters.
 21. A thermoadhesive and thermomoldable structuralmaterial for successive lamination having a composition according toclaim
 2. 22. A three dimensional decorative element based on materialaccording to claim
 21. 23. A laminated part for single use framing inthe molding of reinforced polyester resins, based on material accordingto claim
 1. 24. A rigid bandage made by circular lamination aftertemperature treatment of a strip material according to claim
 1. 25. Asoft bandage made by circular lamination after temperature treatment ofa strip material according to claim
 1. 26. A supporting orimmobilization device obtained by lamination at temperature of a sheetor plaque material according to claim
 1. 27. A process allowing toobtain a composite combination of materials in flat or wound sheetoffering uniformly distributed openings of size from 1 to 12 mm. leavinga free passage of at least 20 percent of the total surface, formable andadhesive to themselves at a temperature in the temperature interval from35° C. to 90° C., and combining an open mesh textile substrate withspecific weight not exceeding 500 g per square meter, whose body issuccessively impregnated or coated, then impregnated again andcompletely covered with at least two distinct materials, the first one,inside or on the surface of the substrate being of the group of polymershaving a softening temperature not exceeding 80° C. and showing abovethat softening temperature a viscoelastic to rubbery but non fluidbehavior, and the last one at the outer surface of the first ones, beingof the group of semi crystalline polymers with a content of aliphaticester type structural units of at least 80 per-cent and having a meltingtemperature comprised between 35° and 80° C. and having during a certaintime after the fusion of an adhesive character on itself in a way thecombination can be laminated in 2 or more layers,wherein the firstmaterial is a) a vinyl polymer or copolymer, b) a polymer or copolymerof acrylic or methacrylic ester, c) a polymer or copolymer of butadiene,chloroprene or isoprene, d) a copolymer of styrene or acrylonitrile withbutadiene or chloroprene or isoprene, e) a copolymer of ethylene andacrylic, methacrylic or vinyl ester, f) a thermoplastic polyurethane, g)a polyurethane or polyurea or h) a branched or partially or totallycross-linked polymer having in proportion larger than 50 percent thestructural unit of crystalizable aliphatic polyesters, wherein the firstmaterial is in whole or in part applied onto the substrate by layeringor impregnation with or without a solvent, of a monomer or macromerreactive composition which is transformed in said material in thepresence of the substrate, said eventual solvent is evaporated.
 28. Aprocess allowing to obtain a composite combination of materials in flator wound sheet offering uniformly distributed openings of size from 1 to12 mm. leaving a free passage of at least 20 percent of the totalsurface, formable and adhesive to themselves at a temperature in thetemperature interval from 35° C. to 90° C., and combining an open meshtextile substrate with specific weight not exceeding 500 g per squaremeter, whose body is successively impregnated or coated, thenimpregnated again and completely covered with at least two distinctmaterials, the first one, inside or on the surface of the substratebeing of the group of polymers having a softening temperature notexceeding 80° C. and showing above that softening temperature aviscoelastic to rubbery but non fluid behavior, and the last one at theouter surface of the first ones, being of the group of semi crystallinepolymers with a content of aliphatic ester type structural units of atleast 80 percent and having a melting temperature comprised between 35°and 80° C. and having during a certain time after the fusion of anadhesive character on itself in a away the combination can be laminatedin 2 or more layers,wherein the first material is a) a vinyl polymer orcopolymer, b) a polymer or copolymer of acrylic or methacrylic ester, c)a polymer or copolymer of butadiene, chloroprene or isoprene, d) acopolymer of styrene or acrylonitrile with butadiene or chloroprene orisoprene, e) a copolymer of ethylene and acrylic, methacrylic or vinylester, f) a thermoplastic polyurethane, g) a polyurethane or polyurea orh) a branched or partially or totally cross-linked polymer having inproportion larger than 50 percent the structural unit of crystalizablealiphatic polyesters, wherein the first material is in whole or in partapplied onto the substrate by layering or impregnation of a polymerlatex followed by the evaporation of the water it contains at atemperature that allows the coalescence of the polymer particles.